Cyclobutenedione derivative, manufacturing method thereof and non-linear optical device containing the same

ABSTRACT

A cyclobutenedione derivative. It comprises substituted or non-substituted aromatic group A; conjugated chain B which may contain an aromatic bonding group; and hydrogen bonding or ion bonding cyclobutenedionyl group C having an aromatic group which is bonded to the conjugated chain B, wherein A and B and C are bonded in the form of A-B-C. Crystal of the derivative is used as a non-linear optical device.

This is a Division of application Ser. No. 08/939,818 filed Sep. 29,1997, now U.S. Pat. No. 5,861,514 which in turn is a Division ofapplication Ser. No. 08/706,778 filed Sep. 3, 1996 now U.S. Pat. No.5,726,317. The entire disclosures of the prior applications are herebyincorporated by reference herein in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel cyclobutenedione derivativethat is advantageous to serve as a non-linear optical material, amanufacturing method therefor and a non-linear optical device using thesame.

2. Description of Related Art

In the fields of optical communication and optical information process,non-linear optical devices play important roles. Non-linear opticalmaterials for use in the non-linear optical devices are a significantlyimportant substance for realizing optical signal processing, such asphotomixing for generating the frequency which is the sum of or thedifference between two types of incident light beams having differentfrequencies, optical parametric generation, with which the frequency ofa new generated lightwave is parametrically dependent on that of anoriginal light source, the Pockels effect and the Kerr effect obtainabledue to change in the refractive index of an optical medium, conversionof incident light into the second harmonic component (SHG) or the thirdharmonic component (THG) and a memory effect obtainable from opticalbistability.

Hitherto, inorganic compounds have been employed as the material for thenon-linear optical devices of the foregoing type. Although crystal ofinorganic compounds, such as potassium titanium phosphate (KTP: KTiOPO₄)and lithium niobate (LN: LiNbO₃), has been known, characteristicsrequired to realize the foregoing purposes have not been satisfied.

On the other hand, organic non-linear optical materials have attractedattention in recent years as new optical device materials in theoptoelectronic industrial field and, thus, the materials haveenergetically been developed and researched. In particular, compounds ofa type having electron donative groups and electron accepting groups intheir π electron conjugated system have been known to have strongoptical non-linear characteristic, at the molecule level, due to theinteraction of the laser beams as electromagnetic waves and π electronslocally present in the molecules.

There have been researched, for example, 2-methyl-4-nitroaniline,m-nitroaniline, N-(4-nitrophenyl)-L-prolinol,4-dimethylamino-4'-nitrostilbene and 4'-nitrobenzylidene-4-nitroaniline.

These materials are, similarly to inorganic materials, usually used in asingle crystal state. In order to exhibit secondary non-linear opticaleffect in this state, it is essential that the materials do not havecentrally symmetric property. However, the great dipole moment of themolecule raises a problem in that non centrally symmetric crystal cannoteasily be formed as a thermodynamically stable phase.

Although a fact has been known that employment of asymmetric center anduse of hydrogen bonds are effective when a material which can grow intonon centrally symmetric crystal is designed, a general method has notbeen found yet.

Organic crystal cannot easily be allowed to grow largely and obtainedorganic crystal is too brittle, which are peculiar issues for organicsubstances; therefore, there is also a problem in that precise and fineprocess cannot easily be performed. Thus, there arises a requirement fora high performance material necessary to manufacture efficient devices.

In general, the non-linear optical device material is required to havegreat optical non-linear characteristic, excellent processability, heatresistance, stability against environment, light transparency, highdielectric breakdown voltage and stability when irradiated with a laserbeam. However, conventional materials cannot satisfy these requirements.

Accordingly, the inventors of the present invention suggestedcyclobutenedione derivatives represented by the following GeneralFormula (VI) and a non-linear optical device containing the same(JP-A-3-112950). Although the suggested derivatives have a greateroptical non-linear characteristic as compared with conventionalmaterials, a further improved material having great optical non-linearcharacteristic has been required.

As other prior art, the following are know: JP-A-7-309818 andJP-A-7-309819, in which systhesizing method of the compound which mightbe similar to the compound (X) referred to in the present invention andits property are disclosed; and JP-A-8-119914, in which disclosed arethe synthesizing method of the compounds (III), (V) and (VII) referredto in the present invention and properties. ##STR1##

SUMMARY OF THE INVENTION

A first object of the present invention is to provide a novel chemicalsubstance which is capable of solving the foregoing problems, which hasgreater non-linear optical effect, sufficient chemical and thermalstability and satisfactory transparency, which is easy to grow as singlecrystal from a solution state or a molten state and easy to an organicnon-linear optical device.

A second object of the present invention is to provide a method ofmanufacturing the chemical substance of the foregoing type. A thirdobject of the present invention is to provide a non-linear opticaldevice containing the foregoing chemical substance.

The inventors of the present invention have found a compound exhibitingexcellent secondary non-linear optical effect by inducing an appropriatesubstituent into a compound group exhibiting great dipolar moment ofmolecules, f and without the substituent capable of easily forming acentrally symmetric structure when forming crystal. Then, the inventorshave applied the material to an organic non-linear optical device, andhave completed the following invention.

The first aspect of the present invention is a cyclobutenedionederivative comprising: substituted or non-substituted aromatic group A;conjugated chain B which may contain an aromatic bonding group; andhydrogen bonding or ion bonding cyclobutenedionyl group C having anaromatic group which is bonded to the conjugated chain B,

wherein A and B and C are bonded in the form of A-B-C.

A preferred embodiment of the above-mentioned invention is acyclobutenedione derivative, which is represented by the followingGeneral Formula (I): ##STR2## wherein p is 1 or 0, E⁵ is a carbon atomor a nitrogen atom, in the case where E⁵ is a carbon atom, p is 1, D isa substituent having a Hammett substituent constant δ₀ ^(R) which is 0or a negative value, in the case where E⁵ is a nitrogen atom, p is 0, Ris a group represented by the following formula, m' is an integer 1 or2, n' is any one of integers from 0 to 3, l' is any one of integers 0, 1and 2, in the case where l' is 2, two m' in the formula may be the sameor different from each other, and the geometric configuration of thedouble bond is an (E) form, a (Z) form, or a mixture of the (E) and (Z)forms, ##STR3## wherein R¹ in substituent R is an alkyl group having 1to 4 carbon atoms and C* is an asymmetric carbon atom.

The second aspect of the invention is a method of manufacturing acyclobutenedione derivative represented by General Formula (I),comprising the step of allowing a cyclobutenedione derivativerepresented by the following General Formula (III) and a compoundrepresented by the following General Formula (IV) to react with eachother: ##STR4## wherein X is a halogen atom, R¹ is an alkyl group having1 to 4 carbon atoms and C* is an asymmetric carbon atom, ##STR5## whichis an (E) form, a (Z) form, or a mixture of the (E) and (Z) forms,wherein p is 1 or 0, E⁵ is a carbon atom or a nitrogen atom, in the casewhere E⁵ is a carbon atom, p is 1, D is a substituent having a Hammettsubstituent constant δ₀ ^(R) which is 0 or a negative value, in the casewhere E⁵ is a nitrogen atom, p is 0 or 1, when pis 1, D is an allylgroup with or without substituents, and there is a suitable negativecharged ion exsisting for the sake of neutrization of positive chargeexisting or a nitrogen atom, m' is an integer 1 or 2, n' is any one ofintegers from 0 to 3, l' is any one of integers 0, 1 and 2, and in thecase where l' is 2, two m' in the formula may be the same of differentfrom each other, ##STR6## which is an (E) form, a (Z) form, or a mixtureof the (E) and (Z) forms, wherein p is 1 or 0, E⁵ is a carbon atom or anitrogen atom, in the case where E⁵ is a carbon atom, p is 1, D is asubstituent having a Hammett substituent constant δ₀ ^(R) which is 0 ora negative value, in the case where E⁵ is a nitrogen atom, p is 0, m' isan integer 1 or 2, n' is any one of integers from 0 to 3, l' is any oneof integers 0, 1 and 2, in the case where l' is 2, two m' in the formulamay be the same or different from each other, R¹ is an alkyl grouphaving 1 to 4 carbon atoms and C* is an asymmetric carbon atom.

The third aspect of the invention is a method of manufacturing acyclobutenedione derivative, comprising the steps of reacting acyclobutenedione derivative represented by the following General Formula(VII) with a pyridine derivative represented by the following GeneralFormula (IVa) to obtain a product represented by the following GeneralFormula (VIII), and reacting the product with alkylhalide represented bythe following General Formula (1X), thereby obtaining a cyclobutenedionederivative represented by General Formula (II): ##STR7## wherein X is ahalogen atom and R² is an alkyl group having 1 to 4 carbon atoms,##STR8## which is an (E) form, a (Z) form, or a mixture of the (E) and(Z) forms, wherein m' and n' are the same as defined above, ##STR9##which is an (E) form, a (Z) form, or a mixture of the (E) and (Z) forms,wherein R² is an alkyl group having 1 to 4 carbon atoms m' is an integer1 or 2, n' is any one of integers from 0 to 3, l' is any one of integers0, 1 and 2, in the case where l' is 2, two m' in the formula may be thesame or different from each other,

    R.sup.3 --X                                                General Formula (IX)

wherein X is a halogen atom and R³ is an alkyl group having 1 to 4carbon atoms ##STR10## which is an (E) form, a (Z) form, or a mixture ofthe (E) and (Z) forms, wherein R² and R³ are each independently an alkylgroup having 1 to 4 carbon atoms, X is a halogen atom, m' is an integer1 or 2, n' is any one of integers from 0 to 3, l' is any one of integers0, 1 and 2, in the case where l' is 2, two m' in the formula may be thesame or different from each other.

The fourth aspect of the invention is a non-linear optical devicewherein a plurality of cyclobutenedione derivative molecules are bound,each of which is represented by the following General Formula (I):##STR11## which is an (E) form, a (Z) form, or a mixture of the (E) and(Z) forms, wherein R is a group represented by the following formula, pis 1 or 0, E⁵ is a carbon atom or a nitrogen atom, in the case where E⁵is a carbon atom, p is 1, D is a substituent having a Hammettsubstituent constant δ₀ ^(R) which is 0 or a negative value, in the casewhere E⁵ is a nitrogen atom, p is 0, m' is an integer 1 or 2, n' is anyone of integers from 0 to 3, l' is any one of integers 0, 1 and 2, inthe case where l' is 2, two m' in the formula may be the same ordifferent from each other, ##STR12## wherein R¹ in substituent R is analkyl group having 1 to 4 carbon atoms and C* is an asymmetric carbonatom.

The inventors of the present invention have investigated organiccompounds including the cyclobutenedione derivative previouslysuggested, suitable for non-linear optical devices, thereby finding thata cyclobutenedione derivative represented by in particular the foregoingformula (I) has significantly great optical non-linear characteristic ascompared with conventional non-linear optical materials. Thus, thepresent invention has been established.

δ₀ ^(R) is a Hammett resonance substituent constant at the p substituentposition.

D is pereferably H, --OR², --NR³ R⁴, or a halogen atom wherein R², R³and R⁴ are each independenty H or an alkyl group having 1-4 carbonatoms. Preferably they are methyl or ethyl. --OR² includes --OCH₃ (δ₀^(R) =-0.43). --NR³ R⁴ includes --N(CH₃)₂ (-0.57), --NH₂ (-0.51).Halogen atoms include I (-0.22), Br(-0.29), Cl(-0.31), and F(-0.48).Other substituents than the above include H(0.0) and --CN(-0.06).Preferable examples of D are H, --OCH₃, --N(CH₃)₂, Br and Cl. Morepreferable is --N(CH₃)₂, which has small δ₀ ^(R) and thus a high electrodonating property.

The cyclobutenedionyl group contained in the cyclobutenedione derivativeexpressed as A-B-C has a great interaction with π electrons in thecompound and exhibits great electron absorbing characteristic due toresonant effect. Therefore, a structure in which the molecule isconsiderably electrically-polarized, can easily be formed, thus causingexcellent optical non-linear characteristic to be realized. Since thiscompound has a long π electron conjugated system expressed as A-B, itexhibits significantly great optical non-linear characteristic ascompared with the cyclobutenedione derivative suggested previously.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram showing an optical system for measuring theoptical non-linear characteristic (the SHG activity) of samples.

PREFERRED EMBODIMENTS OF THE INVENTION

In order to make the present invention effective, portion A ofcyclobutenedione derivative A-B-C is defined as follows: ##STR13##wherein E¹ to E⁵ are each independently a carbon atom permitted to havea nitrogen atom or a substituent, at least two of E¹ to E⁵ are-carbonatoms, in a case where adjacent E¹ and E² or E³ and E⁴ are carbon atomseach having a substituent, the substituents may be connected to form aring, p is 1 or 0, in the case where E⁵ is a carbon atom, p is 1, D is asubstituent having a Hammett substituent constant δ₀ ^(R) which is 0 ora negative value, in the case where E⁵ is a nitrogen atom, p is 0 or 1,in the case where p is 1, D is a substituted or a non-substituted alkylgroup. it this case nitrogen atom represented by E⁵ is positivelycharged. Thus, an appropriate ion having a negative charge is present asa counter ion.

When E⁵ is a carbon atom, p is 1, and D is a substituent having theHammett substituent constant δ₀ ^(R) of 0 or a negative value. Thissubstituent raises the electron density in the overall conjugated systemso that the second order hyperpolarizablity is further raised. If E⁵ isa nitrogen, then p is 0 or 1. If p is 1, then D is a substituted or anon-substituted alkyl group. Also in this case, the effect of theunshared electron pair on the nitrogen or the electron donativecharacteristic of the substituted or non-substituted alkyl group bondedto the nitrogen attains an effect of further raising the second orderhyperpolarizablity of the molecule.

To effectively constitute a long R electron conjugated systemrepresented by A-B in the compound, it is effective for conjugated chainB permitted to contain the foregoing aromatic bonding group to have atleast one molecule structure selected from the group consisting ofmaterials represented by the following general formulas.

    .paren open-st.CH═CH.paren close-st..sub.n,

which is an (E) form, a (Z) form or a mixture of the (E) and (Z) forms

    .paren open-st.C.tbd.C.paren close-st..sub.n

    .paren open-st.N═CH.paren close-st..sub.n,

which is an (E) form, a (Z) form or a mixture of the (E) and (Z) forms##STR14## which is an (E) form, a (Z) form or a mixture of the (E) and(Z) forms, wherein m, n and 1 are each independently the number ofbonding units of the conjugated chain.

By causing hydrogen bonding or ion bonding cyclobutenedionyl group C,having an aromatic group which is bonded to the foregoing conjugatedchain B, to have the structure represented by the following GeneralFormula Cl, the material is cable of effectively exhibiting the opticalnon-linear characteristic of the molecule. ##STR15## wherein R is agroup represented by the following formula ##STR16## wherein R¹ in R isan alkyl group having 1 to 4 carbon atoms and C* is an asymmetric carbonatom.

The chemical structure represented by General Formula (2) makes itpossible to greatly exhibit the optical non-linear characteristicthereof due to conjugation of the benzene ring and the cyclobutenedionestructure. The chemical structure represented by R contributes toeffective arrangement, in crystal, of molecules which respectively havegreat optical non-linear characteristic.

The cyclobutenedione derivatives having these functions includecompounds represented by General Formulas (I) and (Ia): ##STR17##wherein p is 1 or 0, E⁵ is a carbon atom or a nitrogen atom, if E⁵ is acarbon atom, then p is 1, D is a substituent having a Hammettsubstituent constant δ₀ ^(R) which is 0 or a negative value, if E⁵ is anitrogen atom, then p is 0, R is a group represented by the followingformula, m' is an integer 1 or 2, n' is any one of integers from 0 to 3,l' is any one of integers 0, 1 and 2, if l' is 2, then two m' may be thesame or different from each other, and the geometric configuration ofthe double bond is an (E) form, a (Z) form or a mixture of the (Z) and(E) forms. ##STR18## wherein R¹ in the substituent R is an alkyl grouphaving 1 to 4 carbon atoms and C* is an asymmetric carbon atom.##STR19## wherein p is 1 or 0, E⁵ is a carbon atom or a nitrogen atom,if E⁵ is a carbon atom, then p is 1, D is a substituent having a Hammettsubstituent constant δ₀ ^(R) which is 0 or a qnegative value, if E⁵ is anitrogen atom, then p is 0, R is a group represented by the followingformula, m' is an integer 1 or 2, n' is any one of integers from 0 to 3,l' is any one of integers 0, 1 and 2, if l' is 2, then two m' in theformula above may be the same or different from each other, and thegeometric configuration of the double bond is an (E) form, a (Z) form ora mixture of the (Z) and (E) forms. ##STR20## wherein R¹ in thesubstituent R is an alkyl group having 1 to 4 carbon atoms and C* is anasymmetric carbon atom.

The cyclobutenedione derivative represented by the following GeneralFormula (II) included in General Formula (1) is an especially preferredmaterial. ##STR21## wherein R⁵ and R⁶ are each independently an alkylgroup having 1 to 4 carbon atoms, X is a halogen atom, m' is an integer1 or 2, n' is any one of integers from 0 to 3, l' is an integer 1 or 2,if l' is 2, then two m' in the formula above may be the same ordifferent from each other, and geometric configuration of the doublebond is an (E) form, a (Z) form or a mixture of the (Z) and (E) forms.

The compounds represented by General Formula (1) include the followingcompounds. ##STR22## wherein C* is an asymmetric carbon atom. ##STR23##wherein C* is an asymmetric carbon atom. ##STR24## wherein C* is anasymmetric carbon atom. ##STR25## wherein C* is an asymmetric carbonatom. ##STR26## wherein C* is an asymmetric carbon atom. ##STR27##wherein C* is an asymmetric carbon atom. ##STR28## wherein C* is anasymmetric carbon atom. ##STR29## wherein C* is an asymmetric carbonatom. ##STR30## wherein C* is an asymmetric carbon atom. ##STR31##wherein C* is an asymmetric carbon atom. ##STR32##

The cyclobutenedionyl group contained in the cyclobutenedione derivativerepresented by the General Formula (I), as can be understood from themaximum absorption wavelength (the charge transfer zone in the molecule)described in Examples below, has a great interaction with π electrons inthe compound and exhibits great electron absorption due to the resonanceeffect. Therefore, a structure in which the molecule is considerablyelectrically-polarized, can easily be realized, thus causing the greatoptical non-linear characteristic to be realized. Since this compoundhas a long π electron conjugated system, it has a significantly greatoptical non-linear characteristic (second order hyperpolarizablity β is20×10⁻³⁰ esu or higher) as compared with the cyclobutenedione derivativesuggested previously. Therefore, this compound is a preferred materialfor a non-linear optical device.

One type of the cyclobutenedione derivatives represented by the GeneralFormula (I) has amino-alcohol having an asymmetric carbon atom servingas a substituent and introduced thereto. The stereostructure and thehydrogen bond of this substituent enables the orientation of moleculesin crystal to be controlled. Thus, asymmetric molecular orientation withrespect to the center is realized in a molecule of a type having a highdipole efficiency. For this reason, crystal having great opticalnon-linear characteristic can easily be generated.

Another type of the cyclobutenedione derivatives represented by theGeneral Formula (I) has a quaternary pyridinium salt structure. Thismakes it possible to control orientation of molecules in crystal due tothe ionic interaction. As a result, crystal having great opticalnon-linear characteristic can easily be generated.

The cyclobutenedione derivative represented by the foregoing GeneralFormula (I) can easily be prepared by the following reaction with anexcellent yield. In item A) concerned chemical formulas are illustrated,and in item B) the reaction is explained. ##STR33## wherein X is ahalogen atom, R¹ is an alkyl group having 1 to 4 carbon atoms and C* isan asymmetric carbon atom. ##STR34## which is an (E) form, a (Z) form ora mixture of the (Z) and (E) forms, wherein p is 1 or 0, E⁵ is a carbonatom or a nitrogen atom, if E⁵ is a carbon atom, then p is 1, D is asubstituent having a Hammett substituent constant δ₀ ^(R) which is 0 ora negative value, if E⁵ is a nitrogen atom, then p is 0, m' is aninteger 1 or 2, n' is any one of integers from 0 to 3, l' is an integer0, 1 or 2, and if l' is 2, then two m' in the formula above may be thesame or different from each other. ##STR35## which is an (E) form, a (Z)form or a mixture of the (Z) and (E) forms, wherein p is 1 or 0, E⁵ is acarbon atom or a nitrogen atom, if E⁵ is a carbon atom, then p is 1, Dis a substituent having a Hammett substituent constant δ₀ ^(R) which is0 or a negative value, if E⁵ is a nitrogen atom, then p is 0, m' is aninteger 1 or 2, n' is any one of integers from 0 to 3, l' is an integer0, 1 or 2, if l' is 2, then two m' in the formula above may be the sameor different from each other, R¹ is an alkyl group having 1 to 4 carbonatoms and C* is an asymmetric carbon atom.

B) Initially, the cyclobutenedione derivative represented by the GeneralFormula (III) is dissolved in a solvent, such as N,N-dimethylformamide,N,N-dimethylacetoamide, N-methylpyrolidone or dimethylsulfoxide. Then,compound (IV) in a little excess of the quantity of the cyclobutenedionederivative is, together with palladium complex catalyst and an acidacceptor, added to the obtained solution, followed by heating andpermitting reactions to take place. The palladium complex catalyst maybe any one of known materials having catalyst activity with respect tothe coupling reaction between an aryl halide and a diene compound, thematerials including tetrakis (triphenylphosphine) palladium (0),tetrakis (tri-o-tolylphosphine) palladium (0), dichloro-bis(triphenylphosphine) palladium (II) and bis [1,2-di (diphenylphosphino)ethane] palladium (0) (R, F. Heck, "Palladium Reagents in OrganicSyntheses", Academic Press, London (1985)). The quantity of the catalystmay be changed from 1/1000 equivalent to 1 equivalent with respect tothe cyclobutenedione derivative represented by the foregoing GeneralFormula (II). It is preferable that the quantity of the catalyst be in arange from 1/100 equivalent to 5/100 equivalent with respect to thecyclobutenedione derivative represented by the General Formula (II). Thereason for the limitation of the preferred quantity of the catalyst isas follows. If the quantity is considerably smaller than 1/100equivalent, the catalyst activity deteriorates. If the quantity isconsiderably larger than 5/100 equivalent, the product and the catalystcannot easily be separated from each other. Thus, the yield of theproduct (I) deteriorates. In place of the palladium complex catalyst, anorganic or inorganic bivalent palladium compound, such as palladiumchloride (II) or palladium acetate (II) and a phosphine compound, suchas triphenylphosphine or tri-o-tolylphosphine or1,2-di(diphenylphosphino)ethane, may be separately charged into thesystem to cause a similar reaction to proceed with a satisfactory yield.As for the quantity of the phosphine compound, the reaction generallyproceeds at a maximum yield in the case where the number of phosphorusatoms is 4 to 6 equivalents with respect to palladium. However, thereaction proceeds at a satisfactory yield even if the quantity of thephosphine compound is out of the foregoing range, depending upon thetype of the palladium compound. The acid acceptor may be a known acidacceptor, for example, triethylamine, tributylamine,1,8-diaza[5,4,0]bicycloundecene-7,1,8-bis (dimethylamino) naphthalene,potassium carbonate or sodium acetate. The most satisfactory yield isrealized when the quantity of the acid acceptor is from 1.2 times to 1.5times the quantity of the cyclobutenedione derivative represented by theforegoing General Formula (II); however, the reaction proceeds at asatisfactory yield even if the quantity of the acid acceptor isconsiderably larger or smaller than the foregoing quantity (even if theacid acceptor is not used, in some special cases), depending upon thecombination with the catalyst. The reaction proceeds at a temperature ina range from 40° C. to 200° C. It is preferable that the reactiontemperature be set to 90° C. to 120° C. in view of realizing asatisfactory yield.

The cyclobutenedione derivative represented by the foregoing formula (I)can be also prepared easily and at a satisfactory yield by the followingreaction. ##STR36## wherein X is a halogen atom, Y is a chlorine atom, abromine atom, a methoxy group or an ethoxy group) ##STR37## wherein R¹is an alkyl group having 1 to 4 carbon atoms, and C* is an asymmetriccarbon atom. ##STR38## which is an (E) form, a (Z) form or a mixture ofthe (E) and (Z) forms, wherein p, E, D, m', n', l', R¹ and C* are thesame as those described above. ##STR39## which is an (E) form, a (Z)form or a mixture of the (E) and (Z) forms B') Initially, thecyclobutenedione derivative represented by the General Formula (V) isdissolved in a solvent, such as N,N-dimethylformamide,N,N-dimethylacetoamide, N-methylpyrolidone or dimethylsulfoxide. Then,asymmetric 1-amino-2-alcohol (VI) represented by the foregoing GeneralFormula (V) in a little excess is, while being stirred, added thereto sothat the reaction is allowed to proceed.

Then, the above-mentioned (III) in a little excess with respect to theforegoing cyclobutenedione derivative is added to the obtained solution,together with the palladium complex catalyst and the acid acceptor,followed by raising the temperature so that the reaction is allowed toproceed. The type and the quantity of the palladium complex catalyst,those of the acid acceptor and the reaction temperature are the same asthose described above.

The compound having the quaternary pyridinium salt structure among thecompounds represented by the foregoing General Formula (I) can beprepared as follows: ##STR40## wherein X is a halogen atom, R² is analkyl group having 1 to 4 carbon atoms. ##STR41## which is an (E) form,a (Z) form or a mixture of the (E) and (Z) forms, wherein m' and n' arethe same as those described above. ##STR42## which is an (E) form, a (Z)form or a mixture of the (E) and (Z) forms, wherein R² is an alkyl grouphaving 1 to 4 carbon atoms, m is an integer 1' or 2, n' is any one ofintegers from 0 to 3, l' is any one of integers 0, 1 and 2, and if l' is2, two m' in the formula may be the same or different from each other.

    R.sup.3 --X                                                General Formula (IX)

wherein X is a halogen atom and R³ is an alkyl group having 1 to 4carbon atoms. ##STR43## which is an (E) form, a (Z) form or a mixture ofthe (E) and (Z) forms, wherein R² and R³ are each independently an alkylgroup having 1 to 4 carbon atoms, X is a halogen atom, m' is an integer1 or 2, n' is any one of integers from 0 to 3, l' is any one of integers0, 1 and 2, and if l' is 2, then two m' in the formula may be the sameor different from each other.

B") Initially, the compound represented by General Formula (VIII) isprepared from the compound represented by General Formula (VII) and thecompound represented by General Formula (VIa). In this case, thereaction is performed by the same method and in the same condition asthose described above.

Then, the compound represented by foregoing (VIII), alkylhalide (IX) andan acid acceptor are dissolved or suspended in a solvent, such asN,N-dimethylformamide, N,N-dimethylacetoamide, N-methylpyrolidone ordimethylsulfoxide. The overall system is heated to cause the reaction toproceed. After the reaction is completed and in a state where the systemis still hot, insolubles are quickly removed by filtration, followed byallowing the system to stand still. Thus, the cyclobutenedionederivative represented by General Formula (II) can be obtained in theform of crystal. The acid acceptor may be any one of known acidacceptors including triethylamine, tributylamine, pyridine,1,8-diaza[5,4,0]bicycloundeccene-7,1,8-bis(dimethylamino) naphthalene,potassium carbonate or sodium acetate. The most satisfactory yield isrealized when the quantity of the acid acceptor is 1.2 times to 1.5times the quantity of the cyclobutenedione derivative represented by theforegoing General Formula (II); however, the reaction proceeds at asatisfactory yield even if the quantity of the acid acceptor isconsiderably larger or smaller than the foregoing quantity (even if theacid acceptor is not used, in some special cases), depending upon thecombination with the catalyst. The reaction proceeds at a temperature ina range from 100° C. to 200° C. It is preferable that the reactiontemperature be set to 90° C. to 120° C. in view of realizing asatisfactory yield.

According to the present invention, a non-linear optical device, whereina plurality of cyclobutenedione derivative molecules are bound, each ofwhich is represented by the following General Formula (I) is alsoprovided. ##STR44## which is an (E) form, a (Z) form or a mixture of the(E) and (Z) forms, wherein R is a group represented by the followingformula, p is 1 or 0, E⁵ is a carbon atom or a nitrogen atom, if E⁵ isthe carbon atom, then p is 1, D is a substituent having a substituentconstant of 0 or a negative value, if E⁵ is a nitrogen atom, then p is0, m' is an integer 1 or 2, n' is any one of integers from 0 to 3, l' isany one of integers 0, 1 and 2, and if l' is 2, m' in the formula may bethe same or different from each other. ##STR45## wherein R¹ insubstituent R is an alkyl group having 1 to 4 carbon atoms and C* is anasymmetric carbon atom.

A preferred form is as follows:

(i) A non-linear optical device wherein a plurality of thecyclobutenedione derivative molecules are bound, each of which isrepresented by the following General Formula (II): ##STR46## which is an(E) form, a (Z) form or a mixture of the (E) and (Z) forms, wherein R⁵and R⁶ are each independently an alkyl group having 1 to 4 carbon atoms,X is a halogen atom, m' is an integer 1 or 2, n' is any one of integersfrom 0 to 3, l' is any one of integers 0, 1 and 2, and if l' is 2, twom' in the formula may be the same of different from each other.

(ii) A non-linear optical device, which comprises crystal having a noncentrally symmetric structure formed by hydrogen-bonding of molecules ofa compound which is represented by the following General Formula (I) andwhich has a substituent capable of hydrogen-bonding in the 2-position ofits cyclobutenedionyl group, through the substituent: ##STR47## which isan (E) form, a (Z) form, or a mixture of the (E) and (Z) forms, whereinZ is a substituent capable of hydrogen-bonding, D is 1 or 0, E⁵ is acarbon atom or a nitrogen atom, in the case where E⁵ is a carbon atom, pis 1, D is a substituent having a substituent constant which is 0 or anegative value, in the case where E⁵ is a nitrogen atom, p is 0, m' isan integer 1 or 2, n' is any one of integers from 0 to 3, l' is any oneof integers 0, 1 and 2, and in the case where l' is 2, two m' in theformula may be the same or different from each other.

(iii) A non-linear optical device according to the present invention andhaving a second order hyperpolarizablity β of 20×10⁻³⁰ esu or higher.

A representative schematic view, description of the same, and arepresentative manufacturing method will now be described with referenceto the following examples.

Examples of the present invention will now be described.

EXAMPLE 1

Preparation of cyclobutenedione derivative (I-1), the raw material ofwhich is1-(4-iodophenyl)-2-[(r)-2-hydroxypropylamino]-cyclobutene-3,4-dione(II-1) and styrene

3.58 g (10 m mol) of a compound represented by the following structuralformula (II-1), 1.8 g (10.5 m mol) of styrene, 0.116 g (0.1 m mol, whichwas 1% with respect to (II-1)) of tetrakis (triphenylphosphine)palladium and 1.23 g (15 m mol) of sodium acetate were dissolved in 15ml of N,N-dimethylformamide, and then reaction was allowed to take placefor 6 hours at 100° C.

After the reaction was completed, the reaction solution was introducedinto water to cause orange crystal to precipitate, followed byfiltrating the precipitation. Then, the orange crystal wasrecrystallized by using N,N-dimethylformamide so that 3.54 g of1-1-(4"[[2""-(r)-hydroxypropylamino]cyclobutene-3"",4"-dione-1"-yl]phenyl)-4-1(phenyl)-ethylene represented by the following structuralformula (I-1) was obtained. The yield was 88%. The obtained crystal wassubjected to element analysis, thus resulting in C: 73.87% (74.60%), H:6.50% (6.51%) and N: 6.91% (7.04%) (note that parenthesized values arecalculated values). The melting point was >285° C. (decompositiontemperature). The maximum absorption wavelength (λ max) in the methanolsolution was 339.5 nm. ##STR48##

EXAMPLE 2

Preparation of cyclobutenedione derivative (I-2), the raw material ofwhich is1-(4-bromophenyl)-2-[(r)-2-hydroxypropylamino]-cyclobutene-3,4-dione(II-2) and 4-vinylanisole (III-3)

3.09 g (10 m mol) of a compound represented by the following structuralformula (II-2), 1.8 g (10.5 m mol) of 4-vinylanisole (III-3), 0.578 g(0.5 m mol, which was 5%, with respect to (II-2)) of tetrakis(triphenylphosphine) palladium and 3.15 g (15 m mol) of 1,8-bis(dimethylamino) naphthalene were dissolved in 15 ml ofN,N-dimethylformamide, and then reaction was allowed to take place for12 hours at 100° C.

After the reactions was completed, the reaction solution was introducedinto water to cause orange crystal to precipitate, followed byfiltrating the precipitation. Then, the orange crystal wasrecrystallized by using N,N-dimethylformamide so that 1.17 g of1-1-(4"[[2""-(r)-hydroxypropylaminol-cyclobutene-3"",4"-dione-1'-yl]phenyl)-2-(4'"-methoxyphenyl)-ethylenerepresented by the following structural formula (I-2) was obtained. Theyield was 29%. The obtained crystal was subjected to element analysis,thus resulting in C: 72.20% (72.21%). H: 5.81% (5.82%) and N: 3.49%(3.845%) (note that parenthesized values are calculated values). Themelting point was >285° C. (decomposition temperature). The maximumabsorption wavelength (λ max) in the methanol solution was 400.2 nm.##STR49##

EXAMPLE 3

Preparation of cyclobutenedione derivative (I-3), the raw material ofwhich is 1-(4-bromophenyl)-2-ethoxycyclobutene-3,4-dione and4-dimethylaminostyrene 3.28 g (10 m mol) of a cyclobutene compoundrepresented by the following structural formula was dissolved in 15 mlof N,N-dimethylformamide. Then, 0.8 g (10 m mol) of(R)-(-)-1-amino-2-propanol was added thereto, and then the solution wasstirred at room temperature for 30 minutes. Then, 1.8 g (10.5 m mol) of4-dimethylaminophenylstyrene, 0.0225 g (0.5 m mol, which was 5% withrespect to the cyclobutene compound) of palladium acetate, 0.1218 g (2 mmol, which was four times palladium acetate) of tris (o-tolyl) phosphineand 1.23 g (15 m mol) of sodium acetate were added thereto, and thenreaction was caused to take place at 100° C. for four hours.

After the reaction was completed, the reaction solution was introducedinto water to cause orange crystal to precipitate, followed byfiltrating the precipitation. Then, the orange crystal wasrecrystallized by using N,N-dimethylformamide so that 2.98 g of1-1-(4"[[2""-(r)-hydroxypropylamino]-cyclobutene-3"",4"-dione-1"-yl]phenyl)-2-1(4"-dimethylaminophenyl)-ethylenerepresented by the following structural formula (I-3) was obtained. Theyield was 74%. The obtained crystal was subjected to element analysis,thus resulting in C: 73.33% (73.38%), H: 6.430% (6.43%) and N: 7.39%(7.44%) (note that parenthesized values are calculated values). Themelting point was >295° C. (decomposition temperature). The maximumabsorption wavelength (λ max) in the methanol solution was 420.5 nm.##STR50##

EXAMPLES 4-7

A target compound shown in Tables 1A and 1B was prepared in the samemanner as in Example 1-3 except that styrene (III-4)-(III-7) shown inTable 1 was used as an intermediate raw material. The melting point andthe maximum absorption wavelength were measured, and then the elementanalysis was performed, thus obtaining values shown in Table 2.

EXAMPLE 8

Preparation of cyclobutenedione derivative (I'), the raw material ofwhich is1-(4-iodophenyl)-2-[(r)-2-hydroxypropylamino]-cyclobutene-3,4-dione(III-1)

3.57 g (10 m mol) of a compound represented by the following structuralformula (III-1), 1.1 g (10.5 m mol) of 4-vinylpyridine, 0.116 g (0.1 mmol, which was 1% with respect to (III-1)) of tetrakis(triphenylphosphine) palladium and 1.23 g (15 m mol) of sodium acetatewere dissolved in 15 ml of N,N-dimethylformamide, and then reaction wasallowed to take place for 4 hours at 100° C.

After the reaction was completed, the reaction solution was introducedinto water to cause brown crystal to precipitate, followed by filtratingthe precipitation. Then, the brown crystal was recrystallized by usingN,N-dimethylformamide so that 2.94 g of1-(4'[2"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)-ethylenerepresented by the following structural formula (I') was obtained. Theyield was 88%. The obtained crystal was subjected to element analysis,thus resulting in C: 71.56% (71.84%), H: 5.60% (5.43%) and N: 8.11%(8.38%) (note that parenthesized values are calculated values). Themelting point was 265° C. to 267° C. (decomposition also took place).The maximum absorption wavelength (λ max) in the methanol solution was375.5 nm. The diene bond was a trans form. ##STR51##

EXAMPLE 9

Preparation of cyclobutenedione derivative (I'), the raw material ofwhich is1-(4-bromophenyl)-2-[(r)-2-hydroxypropylamino]-cyclobutene-3,4-dione(III-2)

3.10 g (10 m mol) of a compound represented by the foregoing structuralformula (III-2), 1.1 g (10.5 m mol) of 4-vinylpyridine, 0.578 g (0.5 mmol, which was 5% with respect to (III-2)) of tetrakis(triphenylphosphine) palladium and 3.21 g (15 m mol) of 1,8-bis(dimethylamino) naphthalene were dissolved in 15 ml ofN,N-dimethylformamide, and then reaction was allowed to take place for 6hours at 120° C.

After the reactions was completed, the reaction solution was introducedinto water to cause yellow crystal to precipitate, followed byfiltrating the precipitation. Then, the yellow crystal wasrecrystallized by using N,N-dimethylformamide so that 1.07 g of1-(4'[2"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)-ethylenerepresented by the following structural formula (I') was obtained. Theyield was 32%. As a result of the element analysis and measurements ofthe melting point and the absorbance, a conclusion was made such thatthe obtained compound was the same as that obtained in the reactions inExample 8. ##STR52##

EXAMPLE 10

Preparation of cyclobutenedione derivative (I'), the raw material ofwhich is 1-(4-iodophenyl)-2-ethoxy-cyclobutene-3,4-dione (V-1)

3.28 g (10 m mol) of a compound represented by the following structuralformula (V-1) was dissolved in 15 ml of N,N-dimethylformamide. Then, 0.8g (10 m mol) of (R)-(-)-1-amino-2-propanol was added thereto, and thenstirred at room temperature for 30 minutes. Then, 1.1 g (10.5 m mol) of4-vinylpyridine, 0.0225 g (0.5 m mol, which was 5% with respect to(V-1)) of palladium acetate, 0.1218 g (2 m mol, which was four timespalladium acetate) of tris (o-tolyl) phosphine and 1.23 g (15 m mol) ofsodium acetate were added thereto, and then reaction was allowed to takeplace for 4 hours at 100° C.

After the reactions was completed, the reaction solution was introducedinto water to cause orange crystal to precipitate, followed byfiltrating the precipitation. Then, the orange crystal wasrecrystallized by using N,N-dimethylformamide so that 2.67 g of1-(4'[2"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)-ethylenerepresented by the following structural formula (I') was obtained. Theyield was 80%. As a result of the element analysis and measurements ofthe melting point and the absorbance, a conclusion was made such thatthe obtained compound was the same as that obtained in the reactions inExample 8. ##STR53##

EXAMPLE 11

Preparation of cyclobutenedione derivative (VIII-1), the raw material ofwhich is 1-(4-iodophenyl)-2-ethoxycyclobutene-3,4-dione (V-1)

3.28 g (10 m mol) of the compound represented by the followingstructural formula (V-1) was dissolved in 15 ml ofN,N-dimethylformamide. Then, 0.8 g (10 m mol) of n-butylamine was addedthereto, and then stirred at room temperature for 30 minutes. Then, 1.1g (10.5 m mol) of 4-vinylpyridine, 0.0225 g (0.5 m mol, which was 5%,with respect to (V-1)) of palladium acetate, 0.1218 g (2 m mol, whichwas four times palladium acetate) of tris (o-tolyl) phosphine and 1.23 g(15 m mol) of sodium acetate were added thereto, and then reaction wasallowed to take place for 4 hours at 100° C.

After the reaction was completed, the reaction solution was introducedinto water to cause orange crystal to precipitate, followed byfiltrating the precipitation. Then, the orange crystal wasrecrystallized by using N,N-dimethylformamide so that 2.31 g of1-(4'[2"-butylaminocyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)ethylenerepresented by the following structural formula (VIII-1) was obtained.The yield was 70%. The obtained crystal was subjected to elementanalysis, thus resulting in C: 74.79% (75.08%), H: 6.31% (6.06%) and N:8.20% (8.43%) (note that parenthesized values are calculated values).The melting point was from 240° C. to 243° C. (decomposition tookplace). The maximum absorption wavelength (λ max) in the methanolsolution was 375.5 nm. ##STR54##

EXAMPLE 12

Preparation of cyclobutenedione derivative (VIII-1), the raw material ofwhich is 1-(4-bromophenyl)-2-butylaminocyclobutene-3,4-dione

3.09 g (10 m mol) of the compound represented by the followingstructural formula, 1.1 g (10.5 m mol) of 4-vinylpyridine, 0.578 g (0.5m mol, which was 5% with respect to the cyclobutene) of tetrakis(triphenylphosphine) palladium and 3.15 g (15 m mol) of 1,8-bis(dimethylamino) naphthalene were dissolved in 15 ml ofdimethylformamide, and then reaction was allowed to take place at 100°C. for 4 hours.

After the reactions was completed, the reaction solution was introducedinto water to cause yellow crystal to precipitate to filtrate theprecipitation. Then, the orange crystal was recrystallized by usingN,N-dimethylformamide so that 1.65 g of1-(4'[2"-butylaminocyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)ethylenerepresented by the foregoing structural formula (VIII-1) was obtained.The yield was 50%. As a result of the element analysis and measurementsof the melting point and the absorbance, a conclusion was made such thatthe obtained compound was the same as that obtained in the reactions inExample 11. ##STR55##

EXAMPLE 13

Preparation of cyclobutenedione derivative (II-13). the raw material ofwhich is1-(4'[2"-butylamino-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)-ethylene(VIII-1)

3.30 g (10 m mol) of a compound represented by the following structuralformula (VIII-1) was dissolved in 5 ml of N-methylpyridine, and then1.64 g (12 m mol) of N-butylbromide was added thereto. Then, reactionwas allowed to take place at 120° C. for 4 hours.

After the reaction was completed, generated orange and needle-shapecrystal was separated by filtration. The obtained crystal wasrecrystallized by using methanol so that 4.22 g of1-(4'[2"-butylamino-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-N-butylpyridinium)-ethylenebromiderepresented by structural formula (I-13) was obtained. The yield was90%. The obtained crystal was subjected to element analysis, thusresulting in C: 63 33.56% (63.97%), H: 6.52% (6.23%), N: 5.90% (5.97%)and Br: 16.58% (17.02%)(note that parenthesized values are calculatedvalues). The melting point was 265° C. to 267° C. (decomposition alsotook place). The maximum absorption wavelength (λ max) in the methanolsolution was 370.8 nm. ##STR56##

EXAMPLE 14

Preparation of cyclobutenedione derivative (I-8), the raw material ofwhich is 1-(4-iodophenyl)-2-[(r)-2-hydroxypropylaminolcyclobutene-3,4-dione (II-1)

3.58 g (10 m mol) of a compound represented by the following structuralformula (II-1), 1.8 g (10.5 m mol) of 1-(4'-dimethylaminophenyl)butadiene (III-1), 0.116 g (0.1 m mol, which was 1% with respect to(II-1)) of tetrakis (triphenylphosphine) palladium and 1.23 g (15 m mol)of sodium acetate were dissolved in 15 ml of N,N-dimethylformamide, andthen reaction was allowed to take place.

After the reaction was completed, reaction solution was introduced intowater so that orange crystal was deposited and then it was separated byfiltration. The precipitation was recrystallized by usingN,N-dimethylformamide so that 3.54 g of1-[4'-{2"-[2'"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1'-yl]phenyl]-4-14""-dimethylaminophenyl)-1,3-butadienerepresented by structural formula (I-8) was obtained. The yield was 88%.The obtained crystal was subjected to element analysis, thus resultingin C: 73.87% (74.60%), H: 6.50% (6.51%) and N: 6.91% (7.04%)(note thatparenthesized values are calculated values). The melting point was >285°C. (decomposition also took place). The maximum absorption wavelength (λmax) in the methanol solution was 439.5 nm. The diene bond was cis/transform. ##STR57##

EXAMPLE 15

Preparation of cyclobutenedione derivative (I-8), the raw material ofwhich is1-(4-bromophenyl)-2-[(r)-2-hydroxypropylamino]-cyclobutene-3,4-dione(II-2)

3.09 g (10 m mol) of a compound represented by the following structuralformula (II-2), 1.8 g (10.5 m mol) of 1-(4'-dimethylaminophenyl)butadiene (III-1), 0.578 g (0.5 m mol, which was 5% with respect to(II-2)) of tetrakis (triphenylphosphine) palladium and 3.15 g (15 m mol)of 1,8-bis (dimethylamino) naphthalene were dissolved in 15 ml ofN,N-dimethylformamide, and then reaction was allowed to take place at100° C. for 12 hours.

After the reaction was completed, the reaction solution was introducedinto water to cause orange crystal to precipitate followed by separatingthe precipitation by filtration. Then, the orange crystal wasrecrystallized by using N,N-dimethylformamide so that 1.17 g of1-[4'-{2"-[2'"-(r)-hydroxypropylaminol-cyclobutene-3",4"-dione-1"-yl]phenyl]-4-14""-dimethylaminophenyl)-1,3-butadienerepresented by the following structural formula (I-8) was obtained. Theyield was 29%. As a result of the element analysis and measurements ofthe melting point and the absorbance, a conclusion was made such thatthe obtained compound was the same as that obtained in the reactions inExample 14. ##STR58##

EXAMPLE 16

Preparation of cyclobutenedione derivative (I-8), the raw material ofwhich is 1-(4-iodophenyl)-2-ethoxycyclobutene-3,4-dione (IV-1)

3.28 g (10 m mol) of a compound represented by the following structuralformula (IV-1) was dissolved in 15 ml of N,N-dimethylformamide. Then,0.8 g (10 m mol) of (R)-(-)-1-amino-2-propanol was added thereto, andthen the solution was stirred at room temperature for 30 minutes. Then,1.8 g (10.5 m mol) of 1-(4'-dimethylaminophenyl) butadiene (III-1),0.0225 g (0.5 m mol, which was 5% with respect to (IV-1)) of palladiumacetate, 0.1218 g (2 m mol, which was 4 times palladium acetate) of tris(o-tolyl) phosphine and 1.23 g (15 m mol) of sodium acetate were addedthereto, and then reaction was allowed to take place at 100° C. for 4hours.

After the reaction was completed, the reaction solution was introducedinto water to cause orange crystal to precipitate, followed byseparating the precipitation by filtration. Then, the orange crystal wasrecrystallized by using N,N-dimethylformamide so that 2.98 g of1-[4'-{2"-[2'"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1"-yl]phenyl]-4-14""-dimethylaminophenyl)-1,3-butadienerepresented by the following structural formula (I-8) was obtained. Theyield was 74%. As a result of the element analysis and measurements ofthe melting point and the absorbance, a conclusion was made such thatthe obtained compound was the same as that obtained in the reactions inExample 14. ##STR59##

EXAMPLE 17

The second order hyperpolarizability β of1-[4'-{2"-[2'"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1"-yl]phenyl]-4-14""-dimethylaminophenyl)-1,3-butadiene[Structural formula (I-8)] prepared in Example 14 was measured. Themeasurement was performed by a Hyper-Rayleigh scattering method [Phys.Rev. Lett., 66,2980 (1991)] suggested by K. Cray and A. Persons et. al.,the measurement being performed in methanol. A value of β of 1700×10⁻³⁰esu was obtained. On the other hand, a similar measurement was performedby using, as a sample, p-nitroaniline and1-(4-dimethylaminophenyl)-2-[2-(r)-hydroxypropylamino)-cyclobutene-3,4-dione[structural formula (VII-1)], thus resulting in β being 35×10⁻³⁰ esu and140×10⁻³⁰ esu.

EXAMPLE 18

The second order hyperpolarizability 8 of1-(4'[2"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)-ethylene[Structural formula (I')] prepared in Example 8 was measured. Themeasurement was performed by a Hyper-Rayleigh scattering method [Phys.Rev. Lett., 66,2980 (1991)] suggested by K. Cray and A. Persons et. al.,the measurement being performed in methanol. A value of β of 500×10⁻³⁰esu was obtained.

EXAMPLE 19

The second order hyperpolarizability β of1-(4'[2"-butylamino-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-N-butylpyridium)-ethylenebromide[structural formula (I-13) prepared in Example 13 was measured. Themeasurement was performed similarly to Example 17. Thus, obtained valueβ was 470×10⁻³⁰ esu.

EXAMPLE 20

The second order hyperpolarizability β of each of the compounds preparedin Examples 1 to 7 was measured similar to Example 17. Results are shownin Table 2, with the result of the cyclobutenedione prepared in Example14.

Measurement of SHG activity:

EXAMPLE 21

Powder of1-[4'-{2"-[2'"-(r)-hydroxypropylamino]cyclobutene-3",4"-dione-1"-yl]phenyl]-4-14""-dimethylaminophenyl)-1,3-butadieneprepared in Example 14 was filled in a glass cell, and then irradiatedwith Nd dope YAG laser (wavelength was 1.064 μm and output was 180mJ/pulse). As a result, green scattered light having a wavelength of 532nm, which was a secondary harmonic wave of the laser, was generated. Itsintensity was about 30 times that measured when urea powder was used asa sample.

EXAMPLE 22

Powder of1-(4'[2"-(r)-hydroxypropylamino]-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-pyridyl)-ethylene[structural formula (I')] prepared in Example 8 was filled in a glasscell, and then irradiated with Nd dope YAG laser (wavelength was 1.064μand output was 180 mJ/pulse). As a result, green scattered light havinga wavelength of 532 nm, which was a secondary harmonic wave of thelaser, was generated. Its intensity was about 30 times that measuredwhen urea powder was used as the sample.

EXAMPLE 23

Powder of1-(4'[2"-butylamino-cyclobutene-3",4"-dione-1"-yl]phenyl)-2-(4'"-N-butylpyridinium)-ethylenebromide[structural formula (I-13)] prepared in Example 13 was filled in a glasscell, and then irradiated with Nd dope YAG laser (wavelength was 1.064μm and output was 180 mJ/pulse). As a result, green scattered lighthaving a wavelength of 532 nm, which was a secondary harmonic wave ofthe laser, was generated. Its intensity was about 25 times that measuredwhen urea powder was used as a sample.

EXAMPLE 24

About the cyclobutene derivatives prepared in Examples 1-7, thenon-linear property (SHG activity) of samples thereof was measured.Results are shown in Table 3, with the result of the cyclobuteneprepared in Example 14. Values of SHG activity are those on the basis ofthe value obtained by using urea as a sample.

As seen from Table 3, the cyclobutenedione derivatives according to theinvention exhibited a higher second order hyperpolarizability (β) andnon-linear optical property (SHG activity) than know organic non-linearoptical materials and were useful for organic non-linear opticalmaterials. In particular, the compounds (I-3) and (I-8), which haveN(CH₃)₂ as a subsutituent of D, were excellent.

As above, the cyclobutenedione derivatives according to the inventionhave higher second order hyperpolarizability and non-linear property(SHG activity) than known organic non-linear optical materials.

FIG. 1 is a block diagram showing an optical system employed to measurethe non-linear characteristic (the SHG activity). A sample 12 isirradiated with a light beam having a wavelength of 1.064 μm emittedfrom a Nd dope YAG laser beam unit 11. Green scattered light having awavelength of 532 nm from the sample 12 is introduced into aphotoelectron sensiticizer 16 through a lens 13, a filter 14 and amonochrome meter 15 so that the intensity of green scattered light ismeasured.

                                      TABLE 1A                                    __________________________________________________________________________    COMPOUND (III)    CYCLOBUTENEDIONE DERIVATES (I)                              __________________________________________________________________________                         STR60##                                                                      #STR61##                                                     -                                                                                               STR62##                                                                      #STR63##                                                     -                                                                                               STR64##                                                                      #STR65##                                                     -                                                                                               STR66##                                                                     ##STR67##                                                  __________________________________________________________________________

                                      TABLE 1B                                    __________________________________________________________________________    COMPOUND (III)     CYCLOBUTENEDIONE DERIVATES (I)                             __________________________________________________________________________                          STR68##                                                                      #STR69##                                                  ##STR70##                                                                                         #STR71##                                                    -                                                                                                STR72##                                                                     ##STR73##                                                 __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                        YIELD    M.P.    ELEMENTAL ANALYSIS (CALC.)                                                                        max(in                                   (%)      (° C.)                                                                         C       H     N     C1    MeOH)                              ______________________________________                                        (I-1)                                                                              88      288˜*                                                                           73.87 6.50  6.91  --    339.5                                               (74.60)  (6.51)  (7.04)                                      (I-2)   29     285˜*      72.70    5.81    3.49    --     400.2                                                     (72.71)  (5.82)  (3.85)                                                       (I-3)   74     295˜*                                                       73.33    6.43    7.39                                                     --     420.5                                                    (73.38)  (6.43)  (7.44)                          (I-4)   53     283˜*      73.09    6.11    3.59    --     400.5                                                     (73.19)  (6.14)  (3.71)                                                       (I-5)   58     280˜*                                                       73.55    6.39    3.50                                                     --     400.2                                                    (73.64)  (6.44)  (3.58)                          (I-6)   51     277˜*      72.83    6.90    3.27    --     398.7                                                     (74.05)  (6.71)  (3.45)                                                       (I-7)   72     284˜*                                                       68.11    4.27    3.59                                                     9.29     373.0                                                  (68.57)  (4.93)  (3.81)   (9.64)                 (I-8)   88     288˜*      73.87    6.50    6.91    --     439.5                                                     (74.60)  (6.51)  (7.04)         ______________________________________                                         *With decomposition                                                      

                  TABLE 3                                                         ______________________________________                                        CYCLOBUTENEDIONE                                                                            β     SHG                                                    DERIVATIVES         (×10.sup.-30 esu)  ACTIVITY (TO UREA)             ______________________________________                                        STRUCTURE (I-1)                                                                             320        20                                                     EXAMPLE 1                                                                     STRUCTURE (I-2)     400           60                                          EXAMPLE 2                                                                     STRUCTURE (I-3)     750             50                                        EXAMPLE 3                                                                     STRUCTURE (I-4)     400           60                                          EXAMPLE 4                                                                     STRUCTURE (I-5)     390           50                                          EXAMPLE 5                                                                     STRUCTURE (I-6)     380           10                                          EXAMPLE 6                                                                     STRUCTURE (I-7)     280            15                                         EXAMPLE 7                                                                     STRUCTURE (I-8)     1700           30                                         EXAMPLE 14                                                                  ______________________________________                                    

What is claimed is:
 1. A method of manufacturing a cyclobutenedionecompound represented by Formula (I) ##STR74## which is an (E) form, a(Z) form, or a mixture of the (E) and (Z) forms, wherein p is 1 or 0, E⁵is a carbon atom or a nitrogen atom, in the case where E⁵ is a carbonatom, p is 1, D is a substituent having a Hammett substituent constantδ0^(R) which is 0 or a negative value, in the case where E⁵ is anitrogen atom, p is 0, m' is an integer 1 or 2, n' is any one ofintegers from 0 to 3, l' is any one of integers 0, 1 and 2, in the casewhere l' is 2, two m' in the formula may be the same or different fromeach other, R¹ is an alkyl group having 1 to 4 carbon atoms and C* is anasymmetric carbon atom, comprising the step of allowing acyclobutenedione compound represented by the following Formula (III) anda compound represented by the following Formula (IV) to react with eachother: ##STR75## wherein X is a halogen atom, R¹ is an alkyl grouphaving 1 to 4 carbon atoms and C* is an asymmetric carbon atom,##STR76## which is an (E) form, a (Z) form, or a mixture of the (E) and(Z) forms, wherein p is 1 or 0, E⁵ is a carbon atom or a nitrogen atom,in the case where E⁵ is a carbon atom, p is 1, D is a substituent havinga Hammett substituent constant δ0^(R) which is 0 or a negative value, inthe case where E⁵ is a nitrogen atom, p is 0, m' is an integer 1 or 2,n1 is any one of integers from 0 to 3, l' is any one of integers 0, 1and 2, and in the case where l' is 2, two m' in the formula may be thesame or different from each other.
 2. A method of manufacturing acyclobutenedione compound according to claim 1, comprising the stepsof:reacting a cyclobutenedione compound represented by the followingFormula (V) with asymmetric aminoalcohol represented by the followingFormula (VI); and reacting a compound represented by the followingFormula (IV) with the resultant, thereby obtaining a cyclobutenedionecompound represented by Formula (I): ##STR77## which is an (E) form, a(Z) form, or a mixture of the (E) and (Z) forms, wherein Formula (V) is:##STR78## wherein X is a halogen atom, Y is a chlorine atom, a bromineatom, a methoxy group or an ethoxy group,wherein Formula (VI) is:##STR79## R¹ is an alkyl group having 1 to 4 carbon atoms and C* is anasymmetric carbon atom, wherein Formula (IV) is: ##STR80## which is an(E) form, a (Z) form, or a mixture of the (E) and (Z) forms, wherein p,E⁵, D, m', n', R¹ and C* are the same as those defined as describedabove.
 3. A method of manufacturing a cyclobutenedione compound,comprising the steps of reacting a cyclobutenedione compound representedby the following Formula (VII) with a pyridine compound represented bythe following Formula (IVa) to obtain a product represented by thefollowing Formula (VIII), and reacting the product with alkylhaliderepresented by the following Formula (1X), thereby obtaining acyclobutenedione compound represented by Formula (II);wherein Formula(VII) is: ##STR81## wherein X is a halogen atom and R² is an alkyl grouphaving 1 to 4 carbon atoms, wherein Formula (1Va) is: ##STR82## which isan (E) form, a (Z) form, or a mixture of the (E) and (Z) forms, whereinl' is any one of integers 0, 1 and 2, m' is an integer 1 or 2, and n' isany one of integers from 0 to 3, wherein Formula (VIII) is: ##STR83##which is an (E) form, a (Z) form, or a mixture of the (E) and (Z) forms,wherein R² is an alkyl group having 1 to 4 carbon atoms, m' is aninteger 1 or 2, n' is any one of integers from 0 to 3, l' is any one ofintegers 0, 1 and 2, in the case where l' is 2, two m' in the formulamay be the same or different from each other, wherein Formula (IX) is:

    R.sup.3 --X

where X is a halogen atom and R³ is an alkyl group having 1 to 4 carbonatoms wherein Formula (II) is: ##STR84## which is an (E) form, a (Z)form, or a mixture of the (E) and (Z) forms, wherein R² and R³ are eachindependently an alkyl group having 1 to 4 carbon atoms, X is a halogenatom, m' is an integer 1 or 2, n' is any one of integers from 0 to 3, l'is any one of integers 0, 1 and 2, in the case where l' is 2, two m' inthe formula may be the same or different from each other.